CN115716949B - Oil-resistant rubber core material, oil-resistant rubber core, and preparation method and application thereof - Google Patents
Oil-resistant rubber core material, oil-resistant rubber core, and preparation method and application thereof Download PDFInfo
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention provides an oil-resistant rubber core material, an oil-resistant rubber core, and a preparation method and application thereof. The material comprises the following components in parts by mass: 110 to 145 parts of rubber matrix, 30 to 40 parts of carbon black, 3 to 8 parts of vulcanizing agent, 2 to 3 parts of anti-aging agent, 2 to 3 parts of accelerator, 3 to 5 parts of plasticizer, 5 to 8 parts of lubricant and 3 to 8 parts of heat conducting material. The beneficial effects of the invention include: the oil-resistant rubber core material prepared by the invention is suitable for sulfur-containing oil-gas wells, under-balanced drilling of ocean platforms and pressure-control drilling, the adaptability of the rubber core in oil-based mud slurry is obviously improved, the corrosion of the oil-based mud slurry to rubber can be resisted, and the safety of operation and construction is further increased.
Description
Technical Field
The invention relates to the field of pressure-control drilling construction, in particular to an oil-resistant rubber core material, an oil-resistant rubber core, and a preparation method and application thereof.
Background
At present, petroleum drilling enters a deep well and an ultra-deep well, offshore deep water and deep layer, complex ground conditions and complex stratum, shale gas, geothermal resource exploration and development and other high-difficulty and high-risk drilling operation stages, and increasingly high requirements are put on drilling technology and safety.
The rotary blowout preventer is a key device for pressure-controlled drilling, the rubber core is used as an important sealing element of the rotary blowout preventer, and the rotary blowout preventer is contacted with oil-based slurry liquid for a long time in an oil-based environment, so that the slurry liquid has stronger corrosiveness to rubber and is easy to cause the phenomena of swelling, skinning, hardening and the like of the rubber. In the use process of the rubber core, radial sliding is easy to generate between the rubber core and the drill rod or dynamic sealing is easy to generate between the rubber core and the drill rod, under the working condition, the local temperature of the inner circle of the rubber core is too high, the abrasion of the rubber core is accelerated, and the rubber core material has higher requirements on the temperature resistance and the abrasion resistance.
Chinese patent CN115181343a discloses a preparation method of low temperature resistant and oil resistant rubber, which can maintain good oil resistance and sealing performance at low temperature of-45 degrees, and the preparation method comprises the following steps: the material comprises the following components in parts by weight: taking 100 parts of nitrile rubber, breaking rubber, passing through for 5-6 times, then adding 1-5 parts of fine materials, 15-30 parts of filler carbon black and 10 parts of softener in sequence, adding 1-2 parts of vulcanizing agent, uniformly mixing, discharging slices after passing through for 3 times, setting the temperature of a vulcanizing instrument to 180 ℃, and vulcanizing for 5 minutes.
Chinese patent CN114573890a discloses a hydrogenated nitrile rubber material and a method for preparing the same. The preparation method comprises the following steps: copolymerizing hydrogenated hydroxyl-terminated liquid nitrile rubber and a flexible monomer carrying hydroxyl groups to obtain a copolymer A; the copolymer A is used for modifying the hydrogenated nitrile rubber. The hydrogenated nitrile rubber is modified by copolymerizing the hydrogenated hydroxyl-terminated liquid nitrile rubber and the flexible monomer, so that the oil resistance, the low temperature resistance and the mechanical properties of the hydrogenated nitrile rubber are balanced, and the hydrogenated nitrile rubber material with ultralow glass transition temperature, good oil resistance and good mechanical properties is finally obtained.
The rubber materials prepared by the two patents have good oil resistance, but are not suitable for oil-based mud. Thus, there is a need for a gum core material suitable for oil-based slurry.
Disclosure of Invention
The invention aims to solve at least one of the defects in the prior art, and one of the aims of the invention is to provide an oil-resistant rubber core material with good heat resistance and wear resistance.
In order to achieve the above purpose, the invention provides an oil-resistant rubber core material.
The material comprises the following components in parts by mass: 110 to 145 parts of rubber matrix, 30 to 40 parts of carbon black, 3 to 8 parts of vulcanizing agent, 2 to 3 parts of anti-aging agent, 2 to 3 parts of accelerator, 3 to 5 parts of plasticizer, 5 to 8 parts of lubricant and 3 to 8 parts of heat conducting material.
According to an exemplary embodiment of the present invention, the rubber matrix may include a mixture of hydrogenated nitrile rubber, and acrylate rubber; wherein, the weight portions are 70 to 85 portions of hydrogenated nitrile rubber, 30 to 40 portions of nitrile rubber and 10 to 20 portions of acrylate rubber.
According to an exemplary embodiment of the present invention, the hydrogenated nitrile rubber has a Mooney viscosity number of 35 to 45 as measured at ML (1+4) 100 ℃; and/or the content of acrylonitrile in the hydrogenated nitrile rubber is more than or equal to 45 percent.
According to an exemplary embodiment of the present invention, the comonomer may synthesize the acrylate rubber by one of a solution polymerization method and an emulsion polymerization method.
According to an exemplary embodiment of the present invention, the carbon black may include one or more of spray carbon black, thermal cracking carbon black, and nano white carbon black.
According to an exemplary embodiment of the present invention, the vulcanizing agent may include one of sulfur, DTDM, a vulcanizing resin 2402, and peroxide DCP.
According to an exemplary embodiment of the present invention, the anti-aging agent may include one or more of an anti-aging agent RD, an anti-aging agent D, an anti-aging agent NAPM, and an anti-aging agent OD.
According to an exemplary embodiment of the present invention, the plasticizer may include one or more of aromatic oil, rosin oil, paraffin oil, gu Longma resin, and RX-80.
According to an exemplary embodiment of the invention, the accelerator may include one or more of accelerator CZ, accelerator DZ, accelerator DM, accelerator NA-22, and accelerator TAIC.
According to an exemplary embodiment of the present invention, the lubricant may include one or both of oleamide and nano molybdenum disulfide; wherein the granularity of the molybdenum disulfide is 450-720 meshes.
According to an exemplary embodiment of the present invention, the heat conductive material may be two of carbon nanotubes, graphene, and spherical alumina.
In another aspect, the invention provides a method for preparing an oil resistant rubber core material, the method comprising the steps of: banburying the rubber matrix and the heat conducting material for 3-6 minutes; adding vulcanizing agent, anti-aging agent and accelerator, banburying for 5-8 minutes; adding plasticizer, lubricant and carbon black, banburying for 5-8 minutes, and discharging glue; the glue stock is fed through for 8 to 10 times, and discharged for 2 to 3 times and then is cut off; and standing the rubber material for 16-20 hours, and vulcanizing to obtain the oil-resistant rubber core material.
In yet another aspect, the present invention provides a method for preparing an oil resistant rubber core, the method comprising the steps of: and (3) filling the prepared oil-resistant rubber core material into a mould, and vulcanizing for 5.5-6.5 hours under the conditions of the pressure of 16-20 MPa and the temperature of 150+/-3 ℃ to obtain the oil-resistant rubber core.
In yet another aspect, the invention provides an oil resistant rubber core comprising the oil resistant rubber core prepared by the preparation method of the oil resistant rubber core.
In a final aspect, the present invention provides the use of an oil resistant rubber core as a sealing element in a rotary blowout preventer.
Compared with the prior art, the invention has the beneficial effects that at least one of the following contents is included:
(1) The rubber core material has good physical and mechanical properties, has low mass and volume change rate after being soaked in the oil-based mud slurry, can effectively avoid the influence caused by the geometric size change of the rubber core, and has low physical and mechanical property reduction rate and good adaptability in the oil-based mud slurry.
(2) The rubber core material has excellent temperature resistance and medium resistance.
(3) The rubber core material has excellent wear resistance and corrosion resistance.
(4) The rubber core material has wide adaptability in oil-based mud slurry, and has only tiny volume and mass change rate after being used in oil-based mud slurry with various formulas.
Detailed Description
The present invention will be further described in detail with reference to specific examples, so that those skilled in the art can better understand the present invention.
Rotary blowout preventers are a key device for underbalanced/pressure controlled drilling, and the rubber core made of rubber core material is an important sealing element of the rotary blowout preventers. In an oil-based environment, the rubber core is contacted with oil-based slurry for a long time, the slurry has strong corrosiveness to rubber, and the rubber is easy to swell, peel and harden; in the use process of the rubber core, radial sliding is easy to generate between the rubber core and the drill rod or dynamic sealing is directly performed between the rubber core and the drill rod, under the working condition, the local temperature of the inner circle of the rubber core is too high, the abrasion of the rubber core is accelerated, and higher requirements are provided for the temperature resistance and the abrasion resistance of the rubber core material.
Example embodiment 1
The present exemplary embodiment provides an oil resistant rubber core material.
The material comprises the following components in parts by mass:
110 to 145 parts of rubber base, for example 115 parts, 120 parts, 125 parts, 130 parts, 135 parts, 140 parts;
30 to 40 parts of carbon black, for example, 31 parts, 33 parts, 35 parts, 37 parts, 39 parts;
3 to 8 parts of vulcanizing agent, for example, 4 parts, 5 parts, 6 parts, 7 parts;
2 to 3 parts of anti-aging agent, such as 2.3 parts, 2.5 parts, 2.7 parts, 2.9 parts;
2 to 3 parts of accelerator, for example 2.3 parts, 2.5 parts, 2.7 parts, 2.9 parts;
3 to 5 parts of plasticizer, for example 3.5 parts, 4 parts, 4.5 parts;
5 to 8 parts of lubricant, for example 5.5 parts, 6 parts, 7 parts, 7.5 parts;
3 to 8 parts of heat conducting material, such as 4 parts, 5 parts, 6 parts and 7 parts.
In this embodiment, the rubber matrix may comprise a mixture of hydrogenated nitrile rubber, nitrile rubber and acrylate rubber; wherein, the hydrogenated nitrile rubber is 70 to 85 parts by mass, such as 73 parts, 75 parts, 79 parts, 81 parts and 83 parts; 30 to 40 parts of nitrile rubber, for example 31 parts, 33 parts, 35 parts, 37 parts, 39 parts; 10 to 20 parts of acrylate rubber, for example, 11 parts, 13 parts, 15 parts, 17 parts, 19 parts.
The hydrogenated nitrile rubber, the mixture of the nitrile rubber and the acrylic rubber is used as a rubber matrix, so that the rubber core material has the temperature resistance of the hydrogenated nitrile rubber and the acrylic rubber and has good manufacturability of the nitrile rubber.
Hydrogenated nitrile rubber, nitrile rubber and acrylate rubber are raw rubber, and the elasticity, strength, wear resistance and the like of the material are improved by adding other auxiliary agents.
In this example, the hydrogenated nitrile rubber has a Mooney viscosity number of 35 to 45, for example 37, 39, 41, 43, measured at ML (1+4) 100 ℃. The viscosity value of the hydrogenated nitrile rubber is 35-45, so that the added hydrogenated nitrile rubber has better physical and mechanical properties.
In this example, the acrylonitrile content of the hydrogenated nitrile rubber is greater than or equal to 45%, for example 50%, 55%, 60%, 70%, 80%. The acrylonitrile content is more than or equal to 45 percent to ensure that the rubber core material has enough oil resistance.
In this embodiment, the comonomer of the acrylate rubber may be a low temperature oil resistant monomer.
In this embodiment, the comonomer may synthesize the acrylate rubber by one of a solution polymerization method and an emulsion polymerization method.
In this embodiment, the carbon black may include one or more of spray carbon black, thermal cracking carbon black, and nano white carbon black. Carbon black material is added to increase the abrasion resistance of the rubber.
In this embodiment, the vulcanizing agent may include one of sulfur, DTDM (i.e., 4' -dithiodimorpholine), a vulcanizing resin 2402 (i.e., p-tert-butylphenol resin), and a peroxide DCP (i.e., dicumyl peroxide).
In this embodiment, the anti-aging agent may include one or more of an anti-aging agent RD (i.e., 1, 2-dihydro-2, 4-trimethylquinoline), an anti-aging agent D (i.e., N-phenyl-2-naphthylamine), an anti-aging agent NAPM (i.e., N-4 (anilinophenyl) methacrylamide), and an anti-aging agent OD (i.e., octylated diphenylamine).
In this embodiment, the plasticizer may include one or more of aromatic oil, rosin oil, paraffin oil, gu Longma resin, and RX-80 resin.
In this embodiment, the accelerator may include one or more of accelerator CZ (i.e., N-cyclohexyl-2-benzothiazole sulfenamide), accelerator DZ (i.e., N-dicyclohexyl-2-benzothiazole sulfenamide), accelerator DM (i.e., 2' -dithiodibenzothiazyl), accelerator NA-22 (i.e., 2-imidazolidinone), and accelerator TAIC (i.e., triallyl isocyanurate).
In this embodiment, the lubricant may include one or both of oleamide and nano molybdenum disulfide; wherein the granularity of the molybdenum disulfide is 450-720 meshes. The addition of the lubricant gives the rubber material excellent self-lubricating performance on the basis of the wear resistance of the carbon black.
In this embodiment, the heat conductive material may be two of carbon nanotubes, graphene, and spherical alumina.
In this embodiment, the thermal conductivity of the thermally conductive material is greater than or equal to 400W/mK. The heat conducting material is added to improve the temperature resistance of the rubber core material and prevent the local temperature of the product from being too high.
Example embodiment 2
The embodiment provides a preparation method of an oil-resistant rubber core material.
The method comprises the following steps:
S1, putting the rubber matrix and the heat conducting material into an internal mixer for banburying for 3-6 minutes, for example, 4 minutes and 5 minutes.
S2, adding a vulcanizing agent, an anti-aging agent and an accelerator, and banburying for 5-8 minutes, for example, 6 minutes and 7 minutes.
S3, adding the plasticizer, the lubricant and the carbon black, banburying for 5-8 minutes, and discharging the glue, for example, 6 minutes and 7 minutes.
S4, passing the sizing material on an open mill for 8-10 times, discharging air for 2-3 times, and then discharging the sizing material, for example, passing the sizing material for 9 times.
S5, standing the rubber material for 16-20 hours, and then preparing the oil-resistant rubber core material on a vulcanizing machine, for example, standing for 17 hours, 18 hours and 19 hours.
Example embodiment 3
The embodiment provides a preparation method of an oil-resistant rubber core.
The method comprises the following steps:
The oil-resistant rubber core material prepared in the example 1 or 2 is filled into a mould, and is vulcanized on a vacuum vulcanizing machine with the pressure of 16-20 MPa and the temperature of 150+/-3 ℃ for 5.5-6.5 hours, so as to obtain the oil-resistant rubber core. For example, the pressure is 17MPa, 18MPa, 19MPa; the temperature was 147 ℃, 148 ℃, 149 ℃, 151 ℃, 152 ℃, 153 ℃, and the vulcanization was carried out for 6 hours.
Example embodiment 4
The present exemplary embodiment provides an oil resistant rubber core. The rubber core comprises the oil-resistant rubber core prepared by the preparation method of the oil-resistant rubber core in the example embodiment 4.
In this embodiment, the oil resistant rubber core has a temperature resistance ranging from-30 to 150 ℃, for example, -25 ℃, -10 ℃, -5 ℃, 0 ℃,10 ℃, 30 ℃, 50 ℃, 70 ℃, 90 ℃, 95 ℃, 100 ℃, 120 ℃, 130 ℃, 145 ℃.
Example embodiment 5
The present exemplary embodiment provides for the use of an oil resistant rubber core as a sealing element in a rotary blowout preventer. The performance of the rubber core is controlled from the source, and the oil-resistant rubber core for the rotary blowout preventer is researched, so that the oil-resistant rubber core is suitable for the requirements of sulfur-containing oil-gas wells, ocean platform underbalanced drilling and pressure-control drilling.
The invention analyzes the raw materials and mechanism of the rubber core, controls the performance of the rubber core from the source, and the researched oil-resistant rubber core for the rotary blowout preventer is suitable for the requirements of underbalanced drilling and pressure control drilling of sulfur-containing oil and gas wells and ocean platforms, the adaptability in oil-based slurry is obviously improved, the corrosion of the oil-based slurry to rubber can be resisted, and the safety of operation construction is further increased.
For a better understanding of exemplary embodiments of the present invention, reference is made to the following description in conjunction with specific examples.
Example 1
The rubber core material of the rotary blowout preventer comprises, by weight, 70 parts of hydrogenated nitrile rubber, 30 parts of nitrile rubber, 35 parts of spray carbon black, 5 parts of sulfur, 3 parts of anti-aging agent RD, 3 parts of accelerator DZ, 4 parts of Gu Long Ma resin and 6 parts of oleamide, and is prepared into the rubber core material 1 according to the preparation method of the rubber core material.
Example 2
The rubber core material of the rotary blowout preventer comprises, by weight, 70 parts of hydrogenated nitrile rubber, 30 parts of nitrile rubber, 10 parts of acrylate rubber, 35 parts of spray carbon black, 5 parts of sulfur, 3 parts of an anti-aging agent RD, 3 parts of an accelerator DZ, 4 parts of a Gu Long Ma resin, 6 parts of oleamide, 1 part of a carbon nano tube and 2 parts of graphene, and the rubber core material 2 is prepared according to a preparation method of the rubber core material.
Example 3
The rubber core material of the rotary blowout preventer comprises, by weight, 75 parts of hydrogenated nitrile rubber, 30 parts of nitrile rubber, 20 parts of acrylate rubber, 30 parts of nano white carbon black, 5 parts of vulcanized resin 2402, 3 parts of anti-aging agent RD, 3 parts of accelerator DZ, 2 parts of ancient Long Ma resin, 3 parts of RX-80, 7 parts of nano molybdenum disulfide, 3 parts of graphene and 3 parts of carbon nano tubes, and is prepared into the rubber core material 3 according to a preparation method of the rubber core material.
The gum core materials prepared in examples 1 to 3 were subjected to physical and mechanical property test, abrasion resistance test and liquid resistance test.
The gum core material 1 was tested conventionally and after soaking in an oil-based mud slurry from a mill stream well at 75 c for 64 hours, the results are shown in table 1.
TABLE 1
The gum core material 2 was tested conventionally and after soaking in an oil-based mud slurry from a mill stream well at 75 c for 64 hours, the results are shown in table 2.
TABLE 2
The gum core material 3 was tested conventionally and after soaking in an oil-based mud slurry from a mill stream well at 75 c for 64 hours, the results are shown in table 3.
TABLE 3 Table 3
Comparing the rubber core material 1 and the rubber core material 2, the rubber prepared by adding the heat conducting material carbon nanotubes, graphene and acrylate rubber has improved strength and improved wear resistance; the performance is improved obviously in the aspects of corrosion resistance and temperature resistance of oil-based mud fluid. The material disclosed by the invention is excellent in wear resistance, temperature resistance and corrosion resistance; it is also proved that the carbon nanotubes and the graphene improve the wear resistance and heat resistance of the material, and the addition of the acrylate rubber improves the dielectric resistance of the material.
By comparing the rubber core material 2 and the rubber core material 3, the proportion of the three matrix materials is optimized, the types of other materials are replaced, the materials are optimally prepared, the physical and mechanical properties of the finally prepared rubber material are obviously improved under the same condition, the physical and mechanical properties of the soaked sample are small in change, and the mass and the volume change are tiny. The adaptability in the oil-based mud slurry is also obviously improved, and the corrosion of the oil-based mud slurry to rubber can be basically resisted.
In conclusion, the adaptability of the rubber core in the oil-based slurry is obviously improved, the corrosion of the oil-based slurry to the rubber core can be resisted, and the safety of operation and construction is further improved. The oil-resistant rubber core material prepared by the invention is suitable for underbalanced drilling and pressure-control drilling of sulfur-containing oil-gas wells and ocean platforms.
Although the present invention has been described above by way of the combination of the exemplary embodiments, it should be apparent to those skilled in the art that various modifications and changes can be made to the exemplary embodiments of the present invention without departing from the spirit and scope defined in the appended claims.
Claims (13)
1. The oil-resistant rubber core material is characterized by comprising the following components in parts by mass:
110 to 145 parts of rubber matrix, 30 to 40 parts of carbon black, 3 to 8 parts of vulcanizing agent, 2 to 3 parts of anti-aging agent, 2 to 3 parts of accelerator, 3 to 5 parts of plasticizer, 5 to 8 parts of lubricant and 3 to 8 parts of heat conducting material;
The rubber matrix comprises a mixture of hydrogenated nitrile rubber, nitrile rubber and acrylate rubber; wherein, the hydrogenated nitrile rubber is 70 to 85 parts, the nitrile rubber is 30 to 40 parts and the acrylic rubber is 10 to 20 parts by weight;
The Mooney viscosity value of the hydrogenated nitrile rubber is 35-45 when the ML (1+4) temperature is 100 ℃; the content of acrylonitrile in the hydrogenated nitrile rubber is more than or equal to 45%;
the heat conducting material is two of carbon nano-tubes, graphene and spherical alumina.
2. The oil resistant rubber core material according to claim 1, wherein the comonomer is synthesized into the acrylate rubber by one of a solution polymerization method and an emulsion polymerization method.
3. The oil resistant rubber core material according to claim 1, wherein the carbon black comprises one or more of spray carbon black, thermal cracking carbon black and nano white carbon black.
4. The oil resistant rubber core material according to claim 1, wherein the vulcanizing agent comprises one of sulfur, DTDM, a vulcanizing resin 2402 and peroxide DCP.
5. The oil resistant rubber core material according to claim 1, wherein the anti-aging agent comprises one or more of an anti-aging agent RD, an anti-aging agent D, an anti-aging agent NAPM, and an anti-aging agent OD.
6. The oil resistant gum core material of claim 1, wherein the plasticizer comprises one or more of aromatic oil, rosin oil, paraffin oil, coumarone resin, and RX-80.
7. The oil resistant core material of claim 1 wherein the accelerator comprises one or more of accelerator CZ, accelerator DZ, accelerator DM, accelerator NA-22 and accelerator TAIC.
8. The oil resistant core material of claim 1, wherein the lubricant comprises one or both of oleamide and nano molybdenum disulfide; wherein the granularity of the molybdenum disulfide is 450-720 meshes.
9. A method of preparing an oil resistant gum core material according to any one of claims 1-8, said method comprising the steps of:
Banburying the rubber matrix and the heat conducting material for 3-6 minutes;
adding vulcanizing agent, anti-aging agent and accelerator, banburying for 5-8 minutes;
adding plasticizer, lubricant and carbon black, banburying for 5-8 minutes, and discharging glue;
the glue stock is fed through for 8 to 10 times, and discharged for 2 to 3 times and then is cut off;
and standing the rubber material for 16-20 hours, and vulcanizing to obtain the oil-resistant rubber core material.
10. The preparation method of the oil-resistant rubber core is characterized by comprising the following steps of:
the oil-resistant rubber core material according to any one of claims 1-8 is filled into a mould, and vulcanized for 5.5-6.5 hours under the conditions of the pressure of 16-20 MPa and the temperature of 150+/-3 ℃ to obtain the oil-resistant rubber core.
11. An oil resistant rubber core, which is characterized in that the rubber core is prepared by the preparation method of the oil resistant rubber core in claim 10.
12. The oil resistant rubber core according to claim 11, wherein the oil resistant rubber core has a temperature resistance ranging from-30 to 150 ℃.
13. The use of the oil resistant rubber core of claim 11 as a sealing element in a rotary blowout preventer.
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